Alkoxy vanadyl fluorides and their preparation



United States Patent 3,455,974 ALKOXY VANADYL FLUORIDES AND THEIR PREPARATION Aaron Chung Liong Sn, Wilmington, Del., assignor to E. I. du Pont de Nemonrs and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed June 10, 1966, Ser. No. 556,565 Int. Cl. C07d 105/00; C08f 1/30 US. Cl. 260-429 14 Claims This invention relates to novel organic-soluble alkoxy vanadyl fluorides, to methods of preparing the same and to their use in the coordination catalyzed polymerization of u-olefins.

In general the known fluorine-containing compounds of vanadium are ionic in character and are not soluble in organic solvents. Such compounds have not heretofore been suitable for the preparation of organo-soluble coordination catalysts which are preferred for the preparation of elastomeric copolymers of a-olefins.

A new class of compounds has now been discovered which are fluorine containing vanadyl compounds which are soluble in many aprotic organic solvents. One group of such compounds is described by the formula: v

wherein R and R are alkoxy radicals or B-acyl ketonate radicals or collectively R and R can be an a,w-alkylene dioxy radical. The compounds can have from 2 to 40 carbon atoms but preferably have from 2 to 10 carbon atoms in the molecule. t

Valuable coordination catalysts can be made by mixing at least 2 moles of an organo aluminum compound with 1 mole of the soluble vanadyl fluoride compounds of the present invention.

The above compounds can be made by the following methods: V j

(a) By the metathetical reactions of 2'm0lar proportions of a compound having the formula:

wherein R R and R are alkoxy radicals or R and R are collectively an a,w-alkylene dioXy-radical. R and R can have collectively from 2 to 40 and preferably from 2 to carbon atoms, and R is a lower alkoxy radical; with 1 molar proportion of vanadyl trifluoride in an inert organic solvent at about ambient temperature. A variety of products can be obtained by this method. Thus when R R R VO is a trialkoxy compound, the reaction yields a solution of the dialkoxy vanadyl monofluoride according to the equation: x

wherein R is an alkyl radical.

The product of the reaction is soluble in the preferred solvents whereas vanadyl fluoride is insoluble. Accord: ingly the progress of the reaction is marked 'by the disappearance of the insoluble vanadyl fluoride.

The cyclic orthovanadates i.e. where R and R are collectively an u,w-alkylenedioxy radical can be made by a similar reaction. For example neopentylenedioxy vanadyl fluoride can be prepared by the reaction:

3,455,974 Patented July 15, 1969 0 ahC [(CHahClz'iiOhl The resulting alcohol is removed by azeotropic distillation or by vacuum distillation from the mixture.

(b) By the reaction of vanadyl trifluoride with an alkylene glycol or a,B-diket0ne 'or a metal salt of a diketone, in the presence of an inert organic solvent at about ambient temperatures and removing the hydrogen fluoride formed.

One method of removing hydrogen fluoride is by vacuum stripping of the reaction mixture or by sparging with an inert gas such as nitrorgen. A preferred method is to conduct the reactives in the presence of anhydrous sodium fluoride or potassium fluoride which removes the hydrogen fluoride by forming a double salt MHF .wherein M is Na or K.

This reaction always produces the monofluorovanadium compound regardless of the proportion of reactants employed.

The reactions can be represented by the following equation:

VOF; 2R OOCHzC0R (CHahC 2NaHFg Where Me is a metal of valence n, such as iron; vanadium or aluminum.

(c) Valuable soluble fluorine containing vanadyl compounds can also be made by mixing one molar proportion of VOF with at least two molar proportions of a dialkoxy vanadyl chloride in an inert organic solvent at about ambient temperature. The reaction is believed to be erization of u-Oltsfil'lS with such catalysts. Preferred solvents are aliphtic hydrocarbons, including branched hydrocarbons having from 5 to carbon atoms, cycloaliphatic hydrocarbons such as cyclohexane, benzene hydrocarbons such as benzene, toluene, xylene and the like, and halogenated hydrocarbons such as tetrachloroethylene, methylene dichloride, monochlorobenzene, dichlorobenzene and the like. The chemical nature of the solvent is not important, but the solvent should be convenient to handle for the selected use and should be free of active hydrogen or other groups which could react with the reactants or products described hereinabove.

The reaction to form soluble vanadyl fluoride compounds can be conducted conveniently at room temperature, but higher or lower temperatures can be employed. The preferred range of temperature is from about 0 C. to about 70 C. If desired the compounds can be isolated from the solvent by distillation, preferably under vacuum and preferably at low temperatures and in some cases by crystallization. It has been found that in general the soluble vanadyl fluoride compounds are less stable to temperature than their solutions. The chelated compounds (i.e. those having an a, w-alkylene dioxy substituent) are much more stable than the unchelated alkoxy species.

Since the soluble vanadyl fluoride compounds are readily hydrolysed by water, it is essential to exclude moisture during their preparation and storage. Oxygen should also be excluded, particularly when these materials are employed to form coordination catalysts, since otherwise the activity of the catalysts is diminished. The conventional inert gases can be employed to provide an inert atmosphere over the solution. Nitrogen is typical and is preferred.

AS has been stated hereinabove, valuable coordination catalysts can be made by mixing at least 2 moles of a diorgano aluminum chloride or bromide with one mole of the organo-soluble vanadyl fluoride compounds of the present invention.

The upper limit to the amount of the organoaluminum compound is not critical, 100 moles of the organoaluminum compound per mole of the organo-soluble vanadyl fluoride can be employed. The preferred range is from about 10 to about 50 moles of the diorganoaluminum compound per mole of the organo-soluble vanadyl fluoride compound. The order of addition is not critical; the addition may take place in the presence or absence of monomers, the former method, which gives higher yields, being preferred. The coordination catalysts can be prepared and used in the media which are familiar to those skilled in the coordination catalyst art. Tetrachloroethylene and hexane are representative examples.

The organoaluminum compounds that can be employed as co-catalysts are those customarily employed in the manufacture of coordination catalysts. Preferred compounds can be represented by the formula:

in which R R and R can be C to C alkyl, chlorine or bromine, with the proviso that at least one of R R and R is an alkyl group. Particularly preferred compounds are the dialkyl aluminum chlorides such as diisobutyl aluminum chloride. Mixtures of aluminum compounds can be employed if desired.

The coordination catalyst is frequently used at room temperature but may, when desired, be employed at higher or lower temperatures. The life of the catalyst is longer at lower temperatures; shorter at higher temperatures.

The new vanadium compounds of the present invention, and the catalysts made therefrom are organo-soluble in contrast to other fluorine containing vanadium compounds. The vanadium-fluorine band appears to be appreciably more stable than the vanadium-chlorine band and, in general the fluorine containing vanadium compounds are more stable to hydrolysis and to oxidation than the corresponding chlorine compounds. For example, the compound is a crystalline solid which can be exposed to air at room temperature without change for several days. By contrast the chlorine analog is readily oxidized and hydrolysed so that preparation and retention of a pure sample is difiicult.

This invention is further illustrated by the following specific examples which should not, however, be construed as fully delineating the scope thereof.

EXAMPLES 1-5 General procedure for preparation of organic soluble alkoxy vanadyl fluorides Inside a dry box 0.62 g. (0.005 mole) of vanadyl trifluoride was weighed and put into a -ml. Erlenmeyer flask fitted with a three-way stopcock and containing a magnetic stirring bar. The flask, tightly stoppered, was removed from the dry box. Under a nitrogen stream 39 ml. of hexane and 6 ml. of a 50% solution of triisopropyl orthovanadate in heptane (0.010 gram-mole) were introduced successively into the flask from a hypodermic syringe. The mixture was stirred at room temperature. The vanadyl trifluoride, which is insoluble in non-polar solvents, interacted heterogeneously with the alkyl orthovanadate to give the dialkoxy vanadyl fluoride which is very soluble in non-polar solvents. The completion of reaction was indicated by the disappearance of vanadyl triffuoride from the reaction mixture and the formation of a brown, yellowish solution.

When triisopropyl orthovanadate was employed, hexane was used as the solvent; the formation of diisopropyl vanadyl fluoride was complete in less than two minutes.

When methyl or ethyl orthovanadate were employed, the reaction took place best when benzene was employed as the solvent.

General procedure for the formation of the coordination catalyst in the presence of monomers; preparation of ethylene/propylene/ l,4*hexadiene tripolymer with said catalyst The reactor was a 2-liter 4-neck resin kettle fitted with a thermometer, a mechanical stirrer, a gas inlet and a gas outlet device.

One liter of tetrachloroethylene was introduced into the above reactor at 25 C. and saturated with a mixture of dry ethylene and propylene supplied at the respective rates of 1 l./min. and 3.2 liters/min. While monomer inflow and agitation continuedas before, 0.01 gram-mole of diisobutyl aluminum'monochloride, 0.05 gram-mole of 1,4-hexadiene and 0.001 gram-mole of diisopropoxy vanadyl monofluoride were introduced in turn. The resulting mixture was stirred while the temperature was maintained at 25 C. Aliquots of the; polymer solution were withdrawn at 10-minute intervals with a hypodermic syringe, deactivated with methanol, and concentrated to constant weights for use in reaction rate study. After one hour, the polymerization was terminated by deactivating the catalyst with methanol. After monomer flow had been stopped, the copolymer was precipitated by treating the tetrachloroethylene solution with a large quantity of methanol. A 32-g. yield of ethylene/propylene/ 1,4- hexadiene copolymer was obtained displaying an inherent viscosity of 1.31 (determined on a 0.1% solution in tetrachloroethylene at 30 C.).

Diisobutyl aluminum monochloride was generally added as a l-molar solution in tetrachloroethylene. The diisopropoxy vanadyl fluoride was added as a hexane solution (3 ml. supplying 0.001 gram-mole).

If the catalyst were premixed for 60 seconds in the absence of monomers instead of being made in the presence of monomers, the yield of the tripolymer obtained by the above procedure was decreased by about one-third.

The specific compounds, conditions, and results obtained in Examples 1-5 are given in Table I.

a 50% solution of triisopropyl orthovanadate in n-heptane was introduced in order to destroy any excess vanadyl trifiuoride. The mixture was filtered and the product TABLE I.-PREPARATION OF VANADIUM ALKOXY FLUORIDES AND USE IN POLYME RI- ZATION OF OLEFINS (a) Preparation of Vanadium Alkoxy Fluorides Reaotants Solvent Vanadium Alkoxy Fluoride Product VOFs, Alkoxy Example Mmole Compound Mmole Type Ml. Type Mmole 1 5 VO(O-nBu)a 10 'Ietrachloroethylene..- 43.9 VO(O-nBu) F 15 2 5 V(O-isoPr); l0 Hexane 50 V0(O-iso1 r),F 15 3 VO(O-Et)z do 50 VO(O-Et)nF 15 Tetrachloroethylene... 33.3 2VO(O-isoPr)FCl 4 5 VO(O-isoPr)aC1 10 plus plus Hexane 16 VO(O-isoPr);F 5 5 VO(OMe); 10 Benzene.- 200 V0(OM8)3F (b) Copolymerizatiou of ethylene, propylene and 1,4-hexadiene using coordination catalyst of 0.001 mole vanadium alkoxy fluoride 0.010 mole diisobutyl aluminum chloride 1 liter of tetrachloroethylene as solvent, C. Polymerization for 60 minutes. Ethylene added at l liter/min. Propylene 3.2 liter/min; 1,4-hexadiene 0.05 gram moles.

Polymeric Product, weight percent Example Vanadium Catalyst Component Yield, gm. [1 1mb Propylene 1,4-hexadiene 1 VO(O-nBu);F 25 1.36 42 3 V0 (O-isoPrhF 32 l. 31 53 2 V0 (O-EthF 33 1. 31 50 3. 5 4-- 2V0 (O-isoPr)FCl plus VO(O-lSOP1')zF 29 5 VO(OMe)zF 29 EXAMPLE 6 Polymerization time: E/P/ l, 4-HD copolymer (g./ 25 ml.)

EXAMPLE 7 Preparation of isopropyl-(2,2-dimethyl-1,3-propylene) orthovanadate from neopentyl glycol Under a nitrogen atmosphere 200 ml. of n-hexane and 24 ml. of a 50% solution of triisopropyl orthovanadate in n-heptane (0.04 gram-mole) were added with stirring to 4.16 g. (0.04 gram-mole) of neopentyl glycol in a round-bottom glass flask. The neopentyl glycol, which is only very slightly soluble in hexane, disappeared quickly. The resulting clear, brown, liquid composition was concentrated at 70 C. to a 100-ml. volume, diluted again to 200-ml. volume with hexane, and boiled down again to 100 ml. after being thrice concentrated this way, the solution was finally diluted to a 200 ml. volume with hexane.

Preparation of 2,2-dimethyl-l,3-propylenedioxy vanadyl fluoride residue washed six times with n-hexane and dried for three hours at 0.1 mm. Hg vacuum.

Analysis.-Calculated: Carbon, 31.9; hydrogen, 5.31; vanadium, 27.1. Found: Carbon 32.7; hydrogen, 5.5; vanadium 27.1.

Preparation of ethylene copolymers in the presence of a coordination catalyst made from diisobutyl aluminum monochloride and 2,2 dimethyl 1,3-propylenedi'oxy vanadyl fluoride (A) An ethylene/propylene/1,4-hexadien copolymer was prepared in accordance with the general procedure described in Example 1 except for the following changes: The coordination catalyst was formed by introducing 0.01 gram-mole of diisobutyl aluminum monochloride and .001 gram-mole of 2,2-dimethyl-1,3-propylenedioxy vanadyl fluoride prepared above( introduced as a solution in 6 ml. of methylene chloride). The yield of copolymer after 60 minutes polymerization time was 0.288 g./ 25 ml.

(B) The procedure of Part A was repeated except that 1,4-hexadiene was omitted. The yield of ethylene/propylene copolymer after 60 minutes polymerization time was 0.623 g./25 ml. 7

EXAMPLE 8 Preparation of fiuoro vanadyl bis(acetylacetonate) A 2.06 ml. (0.020 gram-mole) portion of acetylacetone was added from a hypodermic syringe to an agitated suspension of 1.24 g. (0.010 gram-mole) of vanadyl trifiuoride in 250 ml. of benzene at room temperature (25 C.). An intense purple-blue color appeared instantaneously. The agitated mixture was then concentrated by boiling while being swept with a slow stream of nitrogen; the "vapor was acidic indicating HF. When about 200 ml. of solution remained, the temperature was lowered below the 'boiling point and about 1 g. of sodium fluoride was introduced. For 5 minutes the mixture was vigorously stirred. Disappearance of almost all of the vanadyl trifluoride indicated the reaction was essentially complete. Fluoro vanadyl bis(acetylacetonate) was then isolated by concentrating the solution to about 60 ml. and slowly adding hexane to the boiling solution until small particles of solid appeared (about 75 ml. of hexane were needed). After the mixture had been cooled at room temperature,

large glittering crystals formed. The liquid was decanted and the crystals washed with l-hexanezbenzene mixture.

Analysis.-Calculated: Carbon 42.3; hydrogen 4.9; fluorine, 6.7; vanadium, 18. Found: Carbon 42.3, 42.0; hydrogen, 5.2, 4.9; fluorine, 6.7, 6.4; vanadium, 18.4, 18.4.

Preparation of ethylene/ propylene copolymer in the presence of a coordination catalyst made from isobutyl aluminum monochloride and fluoro vanadyl bis(acetylacetonate) Ethylene, propylene, and 1,4-hexadiene were copolymerized in tetrachloroethylene at 25 C. in the presence of a coordination catalyst made by combining 0.005 grammole of diisobutyl aluminum monochloride (in solution in tetrachloroethylene) and 0.0005 gram-mole of fluoro vanadyl bis(acetylacetonate) (10 ml. of a solution made by dissolving 0.541 g., 1.92 gram-moles, in 38.4 ml. of methylene chloride). The general procedure of Example 1 was employed. The following data were obtained:

Grams copolymer/ 25 milliliters Time (minutes) reaction solution The remainder of the solution was concentrated to yield 21 g. of copolymer having an inherent viscosity of 1.7 and analyzing for 49% (by weight) propylene and 3.4% (by weight) 1,4-hexadiene.

The above procedure was repeated except that the temperature was 0 C. The following data was obtained:

Grams copolymer/ 25 milliliters Time (minutes): reaction solution The residual copolymers solution when concentrated gave 36 g. of product.

EXAMPLE 9 Preparation of diethoxy vanadyl fluoride Preparation of premixed catalyst from diisobutyl aluminum monochloride and diethoxy vanadyl fluoride A coordination catalyst was prepared by adding 0.002 gram-mole of diethoxy vanadyl fluoride (3.74 ml. of the solution prepared above) to 0.020 gram-mole of diisobutyl aluminum monochloride (in the form of a l-molar solution in tetrachloroethylene) at about 25 C. The resulting catalyst mixture was agitated for about 60 seconds.

Preparation of ethylene/propylene/ 1,4-hexadiene copolymer with premixed catalyst At the end of the 60-second agitation period described above, a 11.87-ml. portion of the coordination catalyst mixture (containing 0.001 gram-mole of vanadium and 0.010 gram-mole of aluminum) was introduced into an agitated resin kettle containing 1 liter of tetrachloroethylene, 0.05 gram-mole 1,4-hexadiene, and saturation concentrations of ethylene and propylene monomers. The copolymer tion reaction was carried out for 60 minutes at ambient temperature (about 25 C.) whil ethylene and propylene gases were supplied at 1 l./min. and 3.2 l./min., respectively. The ethylene/ propylene/ 1,4-hexadiene tripolymer, isolated by precipitation with methanol, weighed about 22 g.

Preparation of ethylene/propylene/1,4-hexadiene tripolymer with diethoxy vanadyl fluoride/diisobutyl aluminum monochloride coordination catalyst prepared in situ The copolymerization experiment described above was repeated except that the coordination catalyst was made in situ by introducing into the monomer solution in turn diisobutyl aluminum monochloride and diethoxy vanadyl fluoride. The yield of tripolymer was 35 g.

EXAMPLE 10 Preparation of dibutoxy vanadyl fluoride from vanadyl trifluoride and tributyl orthovanadate A 4.2-g. portion of impure vanadyl trifluoride (0.0339 gram-mole) was allowed to interact with 46.2 ml. of heptane solution at 25 C. containing 19.4 g. of tri n-butyl orthovanadate (0.0678 gram-mole). The heptane solution became intensely colored; appreciable quantity of heat was generated. The resulting mixture was diluted to approximately 270 ml. With chlorobenzene while agitated.

The solution prepared above was greenish-brown colored. An appreciable amount of black solid was observed which did not dissolve even after stirring overnight.

Copolymerization of ethylene/propylene/1,4-hexadiene in the presence of a coordination catalyst made in situ from diisobutyl aluminum monochloride and di n-butoxy vanadyl fluoride The apparatus and procedure described in general directions given above before Example 1 were employed. The resin kettle reactor contained 1 l. of tetrachloroethylene at 25 C. and 0.008 gram-mole of 1,4-hexadiene. Ethylene and propylene were continually introduced at the respective rates of 1 l./min. and 3.2 l./min. When the tetrachloroethylene solution had become saturated with ethylene and propylene, the coordination catalyst was formed in situ by successive addition of 0.010 gram-mole of diisobutyl aluminum monochloride and approximately 0.0001 gram-mole of the di n-butoxy vanadyl fluoride prepared above (2.7 ml.). The copolymerization was carried out for minutes at 25 C. Aliquots were removed approximately every 10 minutes and dried to constant weight to give the amount of copolymer formed. The following data were obtained:

eopolymer Wt. Volume (ml.) in Vol. (g.) Wt. (g.)/25 ml.

Time (mins.):

1. An organo-soluble fluorine containing vanadium compound having the formula:

R1 R2'\|7=O i wherein R and R are alkoxy groups,

. CH;|-O\ (011920 /V CH:O F

6. The compound 7. Method of making an organo-soluble fluorine containing vanadium compound which comprises contacting and reacting one molar proportion of vanadyl trifluoride with two molar proportions of a compound having the formula:

in the presence of an inert aprotic solvent at about ambient temperature wherein R R and R are alkoxy groups or where R; and R collectively are an u,w-alkylene dioxy group.

8. Method of claim 7 wherein said solvent roethylene.

9. Method of claim 7 wherein said solvent is hexane.

10. Method of making an organo soluble fluorine-containing vanadium compound which comprises reacting vanadyl trifluoride with a compound selected from an a,w-a1kylene glycol B-diketones or metal salts of fi-diketones in the presence of an inert solvent and removing hydrogen fluoride from the reaction medium.

11. Method of claim 10 wherein said hydrogen fluoride is removed by the addition of anhydrous sodium fluoride or potassium fluoride to the reaction medium.

12. Method of making organo-soluble fluorine containing vanadium compounds which comprises contacting and reacting at least two molar proportions of a compound having the formula:

with 1 molar proportion of vanadyl trifluoride in an inert solvent, wherein R and R are alkoxy groups, which collectively have from 2 to carbon atoms.

13. As a composition of matter, the composition produced according to the method of claim 12.

14. Composition of claim 13 in which R R VOCI is diisopropoxy vanadyl chloride.

is tetrachlo- References Cited FOREIGN PATENTS 1,075,115 1/ 1960 Germany.

TOBIAS E. LEVOW, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R. 

1. AN ORGANO-SOLUBLE FLUORINE CONTAINING VANADIUM COMPOUND HAVING THE FORMULA: 